Materials for imparting water repellency to textile materials and processes for producing and using the same



Patented Jan. 3, 1950 MATERIALS FOR IMPARTING WATER. BE-

PELLENCY To TEXTILE MATERIALS AND PROCESSES FOR PRODUCING AND osmo- THE SAME Mark Pollock and Ernst Zcrner, New York, N. Y., asslgnors to Sun Chemical Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 11, 1946, Serial No. 715,612

18 Claims. '(01. 117-1355) This invention relates to materials and processes for imparting water repellency to textile materials, and to the textile materials treated therewith. More particularly, it relates to products and processes for imparting substantially permanent or durable water repellency to textile materials, and which when used in relatively low but effective concentration does not impair the hand or feel of the treated material.

It is an object of the present invention to provide products of such nature that they impart permanent water repellent characteristics to textile materials treated therewith.

Another object of thepresent invention is to provide products which impart permanent water repellent characteristics to textile materials and which are of such nature that the material treated therewith is substantially neutral upon completion of the treatment and remains substantially neutral thereafter.

Another object of the present invention is to provide processes for preparing such products suitable for imparting permanent water repellent properties to textile materials.

Another object of the present invention is to provide a process for treating textile materials to impart permanent water repellent properties thereto without objectionable effects upon the material treated and to maintain the textile material in a substantially neutral or alkaline condition throughout such treatment and substantially neutral after treatment.

Another object of the present invention is to provide a textile material which is permanently water repellent, which is substantially neutral, and which shows a good hand or feel.

Other objects of the present invention will be apparent from the following description and appended claims.

In connection with the finishing of textile materials, for example, cellulosic textiles, it frequently is desirable to impart water repellent properties thereto. For example, textile materials which are designed for use under conditions where they may be exposed to outside weather conditions such as rain and the like are most useful where they have such properties that they will resist the penetrating and wetting action of water. Such materials include raincoats and sportwear woven from various kinds of textile materials and designed so that the finished prod not can breathe, that is, allow air to pass through the finished materials, but at the same time repel water.

and it is desirable to have the product so prepared that it will retain its water repellent characteristics after being subjected to the ordinary laundering and dry-cleaning operations generally utilized. Water repellent materials which have the characteristics of withstanding laundering and dry-cleaning operations generally are designated as being permanently water repellent, that is, they retain their water repellent characteristics and are not objectionably affected by such cleaning operations.

In accordance with the present invention there are provided products which are satisfactory for imparting water repellent characteristics to textile materials. Further, the textile materials so treated in accordance with the present invention maintain their water repellent characteristics substantially unchanged after being subjected to repeated laundering and dry-cleaning operations, so that the textile material is permanently water repellent. Additionally, the products of the present invention are such that when used to impregnate textiles or fabrics the impregnated fabric is substantially neutral upon completion of the impregnation and drying and curing treating operations without additional treatment, thereby avoiding any objectionable efiects upon the textile material such as tendering which generally is caused by the presence of acidic materials in the textile. Further, no complex operations are required to secure such substantial neutrality of the treated textile material because the characteristics of the impregnating products are such that they require no neutralization steps after impregnation and curing.

The products of the present invention may be utilized to impregnate textiles and impart permanent water repellent properties thereto by application from an aqueous solution which is alkaline in nature. The products of the present invention are adequately and completely dispersible or soluble under such conditions and satisfactorily can be utilized to impregnate the cloth or textile. Because of these characteristics of easy solubility or dispersibility in alkaline aqueous solutions, it is possible to provide a treated material which is substantially neutral without additional operations by utilizing as the alkaline material to secure dispersion or solubility a volatile alkali which is removed from the cloth upon the drying operation which follows impregnation. For example, in the product of the present invention ammonia satisfactorily is utilized to efiect dispersion or solution of the water repellent ma.-

terial in water prior to impregnation of the textile material. Upon completion of the impregnation operation the ammonia is volatilized and removed during the drying and curing step which follows upon the impregnation procedure.

In treating textile material, for example, the water repellent material first is dispersed or dissolved in ammonia water to form an impregnating solution. The textile material then is treated with such solution or dispersion, for example, by passing the textile material through a bath of such water repellent material, subsequently removing excess material, for example, by passing the impregnated textile material through a set of squeeze rolls, and thereafter completing the operation by subjecting the impregnated textile material to a temperature sufflcient to remove therefrom the water taken up by the textile in the impregnation step and likewise sufllcient to complete the effective curing of the material to secure the desired permanent water repellent effect. In this way textile me.- terials are secured which have incorporated therewith a product which imparts permanent water repellent characteristics.

In practicing the present invention an aliphatic nitrile which contains a relatively long, saturated aliphatic hydrocarbon chain, for example, a chain which contains from 12-30 carbon atoms is treated with formaldehyde under conditions such that reaction occurs as hereinafter set out.

The chemical reaction which occurs upon treatment of the nitrile with formaldehyde or a compound which releases formaldehyde is not completely understood. However, it is clear that under the reaction conditions hereinafter set out that a physical change results, indicating clearly that some reaction is effected. Generally it has been found satisfactory in effecting this treatment to admix -12 parts of a material such as paraformaldehyde with 85-100 parts of the aliphatic nitrile. Other materials, such as gaseous formaldehyde or trioxane may be utilized, keeping the proportions of formaldehyde to aliphatic nitrile substantially within the limits above set out.

To initiate the desired reaction the mixture of materials in the proportions set forth above are heated to about 60-65 C., at which point a catalytic quantity of concentrated sulfuric acid is incorporated in the mixture. Immediately upon incorporation of the acid material, the temperature of the admixed materials rises several degrees without additional heating, indicating that a reaction is occurring which is exothermic in nature. At the same time the admixture becomes considerably thicker. The entire admixture is maintained under reactive agitation conditions as by stirring for a period of between 1-4 hours.

been found in. accordance with th present invention that such treatment results in a product which is soluble or dispersible in alkaline solutions and which satisfactorily can be utilized to impregnate textile materials and to impart water repellent properties thereto.

The initial reaction and subsequent treatment with phosphorous trichlorlde also can be 'satisfactorily eilected in the presence of a material which acts as a solvent for the constituents of the reaction. For example, solvents such as ethyl acetate, isopropyl acetate, dioxane, aliphatic or aromatic hydrocarbons, and chlorinated hydrocarbons such as chloroform and carbon tetrachloride may be utilized as solvents.

As catalysts to initiate the reaction between the aliphatic nitrile and formaldehyde or compounds which release formaldehyde an acid such as concentrated sulfuric acid or chlorsulfonic acid may be utilized.

The products secured by the reactions outlined above can be dissolved or dispersed in aqueous alkaline solutions to give a product suitable for impregnating textile materials. The major proportion of the alkaline material used to eii'ect dispersion or solution is a volatile alkali such as ammonia, which will be evaporated upon the heating operation which follows impregnation. This heating operation to effect drying and curing may be performed at a temperature of the order of about 100 to about 180 (7., for example, heating for 5 minutes at 140 to 150 0. having been found satisfactory. In order to obviate the possibility of any residual acidity in the-impregnated and treated fabric material, a small amount of an alkaline material which is not removed during the subsequent heating operation may be incorporated. Examples of such materials include organic bases such as monoethanolamine, diethanolamine, triethanolamine, morpholine and the like.

Examples of illustrative satisfactory material useful for commercial operations in securing permanent water repellent eflects are the following:

Example I In a reaction vessel are placed 85 parts by weight of stearonitrile and 10 parts by weight of paraformaldehyde. The admixture is heated to a temperature of approximately 0., and

Upon completion of such initial reaction the product secured is further reacted with phosphorous trichlorlde to secure a product which is soluble or dispersible in alkali solutions. With products of the nature and in the quantities above set forth, from 3-10 parts of phosphorous trichlorlde generally are satisfactory to effect such further reaction as leads to a product soluble or dispersible in alkali. To facilitate such reaction the admixture is maintained at a tem-, perature of about Gil-65 C. and under reactive agitation conditions, as by stirring, for a period sufilcient to secure solubility or dispersibility of the resulting product in alka which period generally has been found to be about one hour. The reaction which occurs upon treatment with phosphorous trichloride is not clear, but it has maintained under reactive agitation conditions as by stirring. When the temperature is at approximately 65 0., one part of concentrated sulfuric acid is added thereto. No further heat is added to the reaction mixture at this point. The admixture is agitated as long as the temperature continues to rise. With the materials above described it is noted that the temperature rises immediately upon addition of the sulfuric acid and then decreases for a short time and subsequently gradually rises again, reaching a temperature of approximately C. When the temperature no longer rises, the admixture which has become considerably thicker ,and which has lost the grainy appearance imparted by the paraformaldehyde is maintained at a temperature of 60-65" C. for 2 hours. Agitation is continued and 4 parts of phosphorous trichlorlde are added. After addition of the trichlorlde, the mixture is agitated at Gil-65 C. for approximately one hour. The product. obtained is soluble or dispersible in aqueous ammonia solution and can satisfactorily be utilized for treating textile material to impart permanent water repellent characteristics thereto.

material removed by a squeezing operation as by wringer rolls and the impregnated material then dried and cured at 140-150 C. for minutes. The treated material was substantially neutral, was permanently water repellent and showed a good hand.

Example II 100 parts of the nitrile of hydrogenated peanut fatty acids are treated as described in Example I with 12 parts of paraformaldehyde. A similar temperature rise is observed upon addition of sulfuric acid, and after such temperature rise is completed, a solution of 40 parts of candelilla wax in 50 parts of isopropyl acetate is added and agitation continued to effect homogeneity of the mixture, which occurred after approximately 3 hours of stirring. Subsequently parts of phosphorous trichloride are added to the mixture which is maintained at 60 C. and under reactive agitation conditions for one hour. The product obtained is soluble or dispersible in aqueous ammonia solution. Treatment of cloth with such material from aqueous ammonia solution imparts permanent water repellent properties to the cloth.

The wax material utilized serves to impart a somewhat greater initial water repellency to the cloth material, but is not permanently retained by the cloth and is removed in subsequent laundering and cleaning operations.

Other materials which may be utilized in place of the candelilla wax material described include carnauba wax, high melting crystalline mineral waxes, or high melting fatty derivates such as stearamide, octadecylurethane, stearoyl ureaand the like. Such materials impart initially greater water repellency to the cloth material when used in conjunction with the products of the present invention.

Example III A solution of 60 parts of cocoanut fatty acid nitrile, 10 parts of paraformaldehyde and 25 parts of dioxane is placed in a reaction vessel and heated to a temperature of approximately 60 C. The admixture is maintained under reactive agitation conditions and one part of chlorsulfonic acid added thereto. A temperature rise similar to that described in connection with that of Example I is observed and the mixture maintained under reactive agitation conditions, as by stirring, for approximately 2.53 hours. At this point thetemperature of the admixture is brought to 60 C., and 3 parts of phosphorous trichloride added thereto. Agitation is continued until a product soluble or dispersible in ammonia is secured.

In utilizing a product of this example for treatment of textile materials to render the latter water repellent, a mixture of 60 parts of stearoyl urea and 30 parts of dioxane and 100 parts of By practicing the present invention, other advantages in addition to those hereinbefore set out are secured. For example, it is unnecessary to subject the impregnated and cured textile materials of the present invention to a soap or soda ash washing operation, since the treated textile material of the present invention does not have contained therein any additional acidic material which might cause subsequent tendering of the treated textile material. Thus, a substantial operational cost is eliminated, and a simple, economical procedure provided by the present invention.

While the products herein described and the processes of making them constitute preferred embodiments of the invention, changes may be made therein without departing from the scope of the invention as defined in the appended claims.

What is claimed is:

l. A material for imparting permanent water repellent characteristics to textile materials which comprises the complex reaction product secured by reacting under substantially anhy drous conditions an aliphatic acid nitrile of the formula RCEN, where R is an aliphatic group containing 12-20 carbon atoms, with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid to secure an intermediate product, and thereafter reacting said intermediate product with phosphorus trichloride.

2. A material for imparting permanent water.

repellent characteristics to textile materials which comprises the complex reaction product secured by reacting under substantially anhydrous conditions stearonitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid seiected'from the group consisting of sulfuric acid and chlorsulfonic acid to secure an intermediate product, and thereafter reacting said intermediate product with phosphorus trichloride.

3. A material for imparting permanent water repellent characteristics to textile materials which comprises the complex reaction product secured by reacting under substantially anhydrous conditions hydrogenated peanut fatty acid nitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid tov secure an intermediate product, and thereafter reacting said intermediate product with phosphorus trichloride.

'4. A material for imparting permanent water repellent characteristics to textile materials which comprises a complex reaction product secured by reacting under substantially anhydrous conditions cocoanut fatty acid nitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid to secure an intermediate product, and thereafter reacting said intermediate product with phosphorus trichloride.

5. A material for imparting permanent water repellent characteristics to textile materials which comprises the complex reaction product securedby reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CaN, where R is an aliphatic group containing 12-20 carbon atoms, with formaldehyde in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately 60-65 C. to secure an intermediate product, thereafter adding a wax selected from the group consisting of candelilla. carnauba, and high melting crystalline mineral waxes to said intermediate product, and finally reacting the above admixture with phosphorus trichloride at a temperature of approximately 60-65" C. for approximately one hour.

6. The process of preparing a material to impart permanent water repellent characteristics to textile materials treated therewith which comprises the steps of reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CEN, where R is an aliphatic group containing 12-20 carbon atoms with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid, and thereafter reacting the said aldehyde reaction product with phosphorus trichloride.

7. The process of preparing a material to impart permanent water repellent characteristics to textile materials treated therewith which comprises the steps of reacting under substantially anhydrous conditions stearonitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from a group consisting of sulfuric acid and chlorsulfonic acid, and thereafter reacting the said aldehyde reaction product with phosphorus trichloride.

8. The process of preparing a material to impart permanent water repellent characteristics to textile materials treated therewith which comprises the steps of reacting under substantially anhydrous conditions hydrogenated peanut fatty acid nitrile with a material which furnishes formaldehyde under 'the reaction conditions in the presence of a catalytic amount of an acid selected from a group consisting of sulfuric acid and chorsulfonic acid, and thereafter reacting the said aldehyde reaction product with phosphorus trichloride.

9. The process of reparing a material to impart permanent water repellent characteristics to textile materials treated therewith which comprises the steps of reacting under substantially anhydrous conditions cocoanut fatty acid nitriles with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from a group consisting of sulfuric acid and chlorsulfonic acid, and thereafter reacting the said aldehyde reaction product with phosphorus trichloride.

10. The process of preparing a material for imparting permanent water repellent characteristics to textile materials treated therewith which comprises the steps of reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula RC N, where R is an aliphatic group containing 12-20 carbon atoms, with formaldehyde in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately 60-65 C. for approximately 2-3 hours to secure an intermediate prod uct, thereafter adding a wax selected from the group consisting of candelilla, carnauba, and high melting crystalline mineral waxes to said 75 1 monia. of the complex reaction product secured by reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CEN, where R is an aliphatic group containing 12-20 carbon atoms, with a material 15 which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from the group can 7 sisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately 60-65 C. for

approximately 2-3 hours to secure an intermediate product, and reacting said intermediate product with phosphorus trichloride at a temperature of approximately Bil-65 C. for approximately one hour, and thereafter drying and ouring said impregnated textile material at 100- 12. The process of rendering textile materials permanently water repellent which comprises the steps of impregnating said textile material with an aqueous. alkaline dispersion, in which the major proportion of the alkaline material is ammonia, of the complex reaction product secured by reacting under substantially anhydrous conditionsv stearonitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from a group consisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately 60-65 C. for approximately 2-3 hours to secure an intermediate product, and reacting said intermediate product with phosphorus trichloride at a temperature of approximately 60-65 C. for approximately one hour, and thereafter drying and curing said impregnated textile material at IOU-180 C.

13. The process of rendering textile materials permanently water repellent which comprises the steps of impregnating said textile material with an aqueous alkaline dispersion, in which the major proportion of the alkaline material is ammonia, of the complex reaction product secured by reacting under substantially anhydrous conditions hydrogenated peanutfatty acid nitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from a group consisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately -65 C. for approximately one hour to 60 secure an intermediate product, and reacting said intermediate product with phosphorus trichloride, and thereafter drying and curing said impregnated textile material at l00180 C.

14. The process of rendering textile materials permanently water repellent which comprises the steps of impregnating said textile material with an aqueous alkaline dispersion, in which the major proportion of the alkaline material is ammonia, of the complex reaction product secured by reacting under substantially anhydrous conditions cocoanut fatty acid nitrile with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from a. group consisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately 60-6 0. for app oximately 2-3 hours to secure an intermediate product, and reacting said intermediate product with phosphorus trichloride at a temperature of approximately 60-65" C. for approximately one hour, and thereafter drying and curing said impregnated textile material at 100- 180 C.

15. The process of rendering textile materials permanently water repellent which comprises the steps of impregnatingsaid textile material with an aqueous alkaline dispersion, in which the major proportion of the alkaline material is ammonia, of the complex reaction product secured by reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CEN, where R is an aliphatic group containing 12-20 carbon atoms, with a material which furnishes formaldehyde under the reaction conditions in the presence of a catalytic amount of an acid selected from a group consisting of sulfuric acid and chlorsulfonic acid at a temperature of approximately 60-65 C. for approximately 2-3 hours to secure an intermediate product, thereafter adding a wax selected from the group consisting of candelilla, carnauba, and high melting crystalline mineral waxes to said intermediate product, and finally reacting the above admixture with phosphorus trichloride at a temperature of approximately fill-65 C. for approximately one hour, and thereafter drying and curing said impregnated textile material at 100- 180 C.

16. A material for imparting permanent water repellent characteristics to textile materials which comprises the complex reaction product secured by reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CEN, where R is an aliphatic group containing 12-20 carbon atoms, with paraformaldehyde in the presence of a relatively small amount, based upon the amount of nitrile and paraformaldehyde of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid to secure an intermediate product, and thereafter reacting said intermediate product with phosphorus trichloride.

17. A material for imparting permanent water repellent characteristics to textile materials which comprises the complex reaction product secured by reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CEN, where R is an aliphatic group containing 12-20 carbon atoms, with paraformaldehyde in the presence of a catalytic amount of an acid selected from the group consisting of sulfuric and chlorsulfonic acid at a temperature of approximately -65 C. for approximately 2-3 hours to secure an intermediate product, thereafter adding a wax selected from the group consisting of candelilla, carnauba, and high melting crystalline mineral waxes to said intermediate product, and finally reacting the above admixture with phosphorus trichloride at a temperature of approximately 60-65 C. for approximately one hour.

18. The process of rendering textile materials permanently water repellent which comprises the steps of impregnating said textile material with an aqueous ammonia dispersion of the complex reaction product secured by reacting under substantially anhydrous conditions an aliphatic acid nitrile of the formula R-CEN, where R is an aliphatic group containing 12-20 carbon atoms, with a material which furnishes formaldehyde under the reaction conditions in the presence of a relatively small amount, based upon the amount of nitrile and material which furnishes formaldehyde, of an acid selected from the group consisting of sulfuric acid and chlorsulfonic acid at a temperature .of approximately 60-65 C. for approximately 2-3 hours to secure an intermediate product, and reacting said intermediate product with phosphorus trichloride at a temperature of approximately 60-65 C. for approximately one hour, and thereafter drying and curing said impregnated textile material at -180 C.

MARK POI-LOCK. ERNST ZERNER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,175,092 Ralston Oct. 3, 1939 2,261,097 Rust Oct. 28, 1941 2,285,948 Rust June 9, 1942 2,315,135 Rust Mar. 30, 1943 2,333,628 Rust Nov. 2, 1943 2,386,586 Brant Oct. 9, 1945 2,386,631 Pingree Oct. 9, 1945 OTHER REFERENCES Fieser and Fieser Organic Chem." Heath 1944, p. and 204. 

11. THE PROCESS OF RENDERING TEXTILE MATERIALS PERMANENTLY WATER REPELLENT WHICH COMPRISES THE STEPS OF IMPREGNATING SAID TEXTILE MATERIAL WITH AN AQUEOUS ALKALINE DISPERSION, IN WHICH THE MAJOR PROPORTION OF THE ALKALINE MATERIAL IS AMMONIA, OF THE COMPLEX REACTION PRODUCT SECURED BY REACTING UNDER SUBSTANTIALLY ANHYDROUS CONDITIONS AN ALIPHATIC ACID NITRILE OF THE FORMULA R-C$N, WHERE R IS AN ALIPHATIC GROUP CONTAINING 12-20 CARBON ATOMS, WITH A MATERIAL WHICH FURNISHES FORMALDEHYDE UNDER THE REACTION CONDITIONS IN THE PRESENCE OF A CATALYTIC AMOUNT OF AN ACID SELECTED FROM THE GROUP CONSISTING OF SULFURIC ACID AND CHLORSULFONIC ACID AT A TEMPERATURE OF APPROXIMATELY 60-65*C. FOR APPROXIMATELY 2-3 HOURS TO SECURE AN INTERMEDIATE PRODUCT, AND REACTING SAID INTERMEDIATE PRODUCT WITH PHOSPHORUS TRICHLORIDE AT A TEMPERATURE OF APPROXIMATELY 60-65*C. FOR APPROXIMATELY ONE HOUR, AND THEREAFTER DRYING AND CURING SAID IMPREGNATED TEXTILE MATERIAL AT 100180*C. 